Laminate and window film and electronic device

ABSTRACT

A laminate includes a substrate, a self-healing layer on the substrate and having a thickness of greater than or equal to about 50 micrometers, a protective layer between the substrate and the self-healing layer, and a surface layer on the self-healing layer and having a thickness of about 20 nanometers to about 300 nanometers, wherein the self-healing layer has a first elastic modulus and the protective layer has a second elastic modulus, wherein the second elastic modulus is about 1.2 times to about 50 times greater than the first elastic modulus, and wherein the surface layer has a friction coefficient of less than or equal to about 1.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.16/544,957, filed on Aug. 20, 2019, which claims priority to and thebenefit of Korean Patent Application No. 10-2018-0100269, filed in theKorean Intellectual Property Office on Aug. 27, 2018, and all of thebenefits accruing therefrom under 35 U.S.C. § 119, the contents of whichare incorporated herein by reference in their entirety.

BACKGROUND 1. Field

A laminate, a window film including the laminate, and an electronicdevice including the window film are disclosed.

2. Description of the Related Art

A portable electronic device such as a smart phone or a tablet PC mayinclude a window film including a rigid glass substrate or plasticsubstrate for protecting a display module, and a functional layer havingvarious functions may be applied on a surface of the window film.

The use of touch screen panel recognizing a contact position of a fingeror a tool in a smart phone or tablet PC is becoming more prevalent.Accordingly, it would be beneficial to provide an improved window filmcapable of performing various functions.

SUMMARY

An embodiment provides a laminate capable of satisfying desiredmechanical characteristics and surface characteristics.

Another embodiment provides a window film including the laminate.

Yet another embodiment provides an electronic device including thewindow film.

According to an embodiment, a laminate includes a substrate, aself-healing layer on the substrate and having a thickness of greaterthan or equal to about 50 micrometers (μm), a protective layer betweenthe substrate and the self-healing layer, and a surface layer on theself-healing layer and having a thickness of about 20 nm to about 300nm, wherein the self-healing layer has a first elastic modulus and theprotective layer has a second elastic modulus, wherein the secondelastic modulus is about 1.2 times to about 50 times greater than thefirst elastic modulus, and wherein the surface layer has a frictioncoefficient of less than or equal to about 1.

The substrate may include a polymer substrate having a third elasticmodulus and the second elastic modulus may be less than the thirdelastic modulus.

The first elastic modulus may be about 0.1 megapascals (MPa) to about100 MPa.

The protective layer and the self-healing layer may each include apolymer having a cross-linked structure, and a cross-link density of theprotective layer may be greater than a cross-link density of theself-healing layer.

The protective layer and the self-healing layer may each independentlyinclude a cured product of a multi-functional urethane, a cured productof a multi-functional epoxy, a cured product of a multi-functional urea,or a combination thereof.

The self-healing layer may include a cured product of a first urethane(meth)acrylate including a (meth)acrylate group and at least sixurethane groups.

The self-healing layer may further include silica, a metal oxide, asubstituted or unsubstituted polyhedral silsesquioxane, or a combinationthereof.

The protective layer may include a cured product of a second urethane(meth)acrylate including at least two (meth)acrylate groups and at leastone urethane group, wherein the number of the urethane groups in thesecond urethane (meth)acrylate is less than the number of urethanegroups of the first urethane (meth)acrylate.

The protective layer may further include silica, a metal oxide, asubstituted or unsubstituted polyhedral silsesquioxane, or a combinationthereof.

The surface layer may include a cured product of a silicon(meth)acrylate, a cured product of a fluorine (meth)acrylate, a curedproduct of a urethane (meth)acrylate, a cured product of a polyrotaxane,or a combination thereof.

The surface layer may further include silica, a metal oxide, asubstituted or unsubstituted polyhedral silsesquioxane, or a combinationthereof.

The surface layer may include a cured product of polyrotaxane, a curedproduct fluorine (meth)acrylate, and a cured product polyhedralsilsesquioxane.

The protective layer may have a thickness of about 20 μm to about 100μm.

The self-healing layer may have a thickness of about 50 μm to about 100μm.

The second elastic modulus may be about 2 times to about 10 timesgreater than the first elastic modulus.

The substrate may include polyethylene terephthalate, polycarbonate,polyimide, polyamide, polyamideimide or a combination thereof.

The laminate may have a contact angle of greater than or equal to about100 degrees and a pencil hardness of greater than or equal to about 6 Hsimultaneously, wherein the pencil hardness may be a maximum pencilhardness at which a scratch is no longer visible after 3 minutes at 50°C. following formation of the scratch with a load of 1 kg.

According to another embodiment, a window film includes the laminate.

The window film may be a flexible window film.

According to another embodiment, an electronic device includes thewindow film.

The laminate having good mechanical characteristics and surfacecharacteristics, and the window film including the same, are provided.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other advantages and features of this disclosure willbecome more apparent by describing in further detail exemplaryembodiments thereof with reference to the accompanying drawings, inwhich:

FIG. 1 is a cross-sectional view of a laminate according to anembodiment;

FIG. 2 is a cross-sectional view of a display device according to anembodiment; and

FIG. 3 is a cross-sectional view of a display device according toanother embodiment.

DETAILED DESCRIPTION

Example embodiments of the present disclosure will hereinafter bedescribed in detail, and may be easily performed by a person having anordinary skill in the related art. However, actually applied structuresmay be embodied in many different forms, and is not to be construed aslimited to the example embodiments set forth herein. Rather, theseembodiments are provided so that this disclosure will be thorough andcomplete, and will fully convey the scope of the invention to thoseskilled in the art. Like reference numerals refer to like elementsthroughout.

In the drawings, the thickness of layers, films, panels, regions, etc.,are exaggerated for clarity. Like reference numerals designate likeelements throughout the specification. It will be understood that whenan element such as a layer, film, region, or substrate is referred to asbeing “on” another element, it can be directly on the other element orintervening elements may also be present. In contrast, when an elementis referred to as being “directly on” another element, there are nointervening elements present.

In the drawings, parts having no relationship with the description areomitted for clarity of the embodiments, and the same or similarconstituent elements are indicated by the same reference numeralthroughout the specification.

It will be understood that, although the terms “first,” “second,”“third” etc. may be used herein to describe various elements,components, regions, layers and/or sections, these elements, components,regions, layers and/or sections should not be limited by these terms.These terms are only used to distinguish one element, component, region,layer or section from another element, component, region, layer, orsection. Thus, “a first element,” “component,” “region,” “layer,” or“section” discussed below could be termed a second element, component,region, layer, or section without departing from the teachings herein.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms, including “at least one,” unless the content clearly indicatesotherwise. “At least one” is not to be construed as limiting “a” or“an.” “Or” means “and/or.” As used herein, the term “and/or” includesany and all combinations of one or more of the associated listed items.It will be further understood that the terms “comprises” and/or“comprising,” or “includes” and/or “including” when used in thisspecification, specify the presence of stated features, regions,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,regions, integers, steps, operations, elements, components, and/orgroups thereof.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper,” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±30%, 20%, 10% or 5% of the stated value.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this disclosure belongs. It willbe further understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art and thepresent disclosure, and will not be interpreted in an idealized oroverly formal sense unless expressly so defined herein.

Exemplary embodiments are described herein with reference to crosssection illustrations that are schematic illustrations of idealizedembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, embodiments described herein should not beconstrued as limited to the particular shapes of regions as illustratedherein but are to include deviations in shapes that result, for example,from manufacturing. For example, a region illustrated or described asflat may, typically, have rough and/or nonlinear features. Moreover,sharp angles that are illustrated may be rounded. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the precise shape of a region and are notintended to limit the scope of the present claims.

As used herein, unless a definition is otherwise provided, the term“substituted” refers to the replacement of a hydrogen atom of a compoundwith a substituent selected from a halogen atom, a hydroxy group, analkoxy group, a nitro group, a cyano group, an amino group, an azidogroup, an amidino group, a hydrazino group, a hydrazono group, acarbonyl group, a carbamyl group, a thiol group, an ester group, acarboxyl group or a salt thereof, a sulfonic acid group or a saltthereof, a phosphoric acid group or a salt thereof, a C1 to C20 alkylgroup, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30aryl group, a C3 to C30 heteroaryl group, a C7 to C30 arylalkyl group, aC1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30heterocycloalkyl group, and a combination thereof.

As used herein, unless a definition is otherwise provided, the term“hetero” refers to a compound or group including 1 to 4 heteroatoms,wherein the heteroatom is each independently N, O, S, Se, Te, Si, or P.

As used herein, unless a definition is otherwise provided, the term“acryl” refers to an acrylate or methacrylate, or the corresponding acidor salt thereof.

As used herein, the term “cured product” refers to compound that hasbeen subjected to photocuring (e.g., exposure to UV light) or thermalcuring (e.g., exposure to heat) or both for a time sufficient tofacilitate crosslinking or polymerization or both of reactive groups.

Hereinafter, the term “combination” is inclusive of blends, mixtures,alloys, reaction products, stack structures, and the like, and refers totwo or more.

Hereinafter, a laminate according to an embodiment is described.

FIG. 1 is a cross-sectional view of a laminate according to anembodiment.

Referring to FIG. 1, a laminate 10 according to an embodiment includes asubstrate 11, a protective layer 12, a self-healing layer 13, and asurface layer 14.

The substrate 11 may be made of a transparent polymer and may be apolymer film or a copolymer film obtained by polymerization of at leastone monomer and/or oligomer.

The substrate 11 may have a light transmittance of greater than or equalto about 80%, for example greater than or equal to about 85%, in avisible wavelength region of about 380 nanometers (nm) to about 780 nm.The substrate 11 may have a yellowness index (YI, ASTM D1925) of lessthan or equal to about 4.0 (absolute value), for example less than orequal to about 3.5 (absolute value).

The substrate 11 may have an elastic modulus of greater than or equal toabout 1 gigapascal (GPa), for example greater than or equal to about 2GPa, greater than or equal to about 3 GPa, greater than or equal toabout 4 GPa, or greater than or equal to about 5 GPa. For example, thesubstrate 11 may have an elastic modulus of about 1 GPa to about 10 GPa,about 2 GPa to about 9 GPa, about 3 GPa to about 8 GPa, or about 4 GPato about 7 GPa.

The substrate 11 may be made of, for example, polyethyleneterephthalate, polycarbonate, polyimide, polyamide, polyamideimide, or acombination thereof, but is not limited thereto.

The substrate 11 may have, for example, a thickness of about 20micrometers (μm) to about 100 μm. Within the range, the substrate 11 mayhave, for example, a thickness of about 20 μm to about 95 μm, about 25μm to about 95 μm, or about 30 μm to about 95 μm.

The self-healing layer 13 may be disposed on the substrate 11 and mayself-heal damage, such as a scratch, within a relatively short period oftime. The self-healing may be, for example, performed by a hydrogenbonding force, but is not limited thereto.

The self-healing layer 13 may include a polymer having a cross-linkedstructure, for example a cured product of a monomer and/or an oligomerincluding at least one polymerizable group. The self-healing layer 13may include for example a cured product of a urethane having at leastone polymerizable group, a cured product of an epoxy having at least onepolymerizable group, a cured product of a urea having at least onepolymerizable group, or a combination thereof, but is not limitedthereto.

For example, the self-healing layer 13 may include a cured product ofurethane (meth)acrylate having a (meth)acrylate group and a urethanegroup, for example, a cured product obtained by coating a self-healingcomposition including urethane (meth)acrylate having a (meth)acrylategroup and an urethane group and curing the same. The self-healingcomposition may be for example a photocurable composition and/or athermally curable composition.

For example, the urethane (meth)acrylate may have a structure having oneor two (meth)acrylate groups (CH₂═CHC(═O)O— or CH₂═C(CH₃)C(═O)O—) at theterminal end of a core having a urethane moiety. The (meth)acrylategroup at the terminal end may be a cross-linkable functional group andthus may be a chemical crosslinking site. The urethane (meth)acrylatemay have an appropriate cross-linking degree due to the one or two(meth)acrylate groups, and thus the cured product obtained from theself-healing composition may have an appropriate flexibility,elasticity, and hardness and may have foldable, bendable, or rollablecharacteristics.

For example, the urethane (meth)acrylate may have at least six urethanegroups (—NHC(═O)O—), for example, at least three diisocyanate-derivedunits and at least two diol-derived units between the chemicalcrosslinking sites. Such urethane (meth)acrylate may have at least onephysical cross-linking site interposed between chemical crosslinkingsites. When external stress is applied, the bond at the physicalcross-linking site may be broken before the bond at the chemicalcrosslinking site, and the bond at the physical cross-linking site maybe restored by itself. Thus, the physical cross-linking site may be apart that enables self-healing when a scratch occurs. The urethane(meth)acrylate having at least six urethane groups may exhibit aself-healing property at room temperature in a short time after ascratch occurs. Even if a scratch is formed by high pencil hardness of 4H or more, for example 6 H or more, or 8 H or more occur, it may beself-healed.

The urethane (meth)acrylate may include, for example, at least six, atleast seven, at least eight, at least nine, or at least ten urethanegroups, and for example, 100 or less, 60 or less, 40 or less, 20 orless, or 14 or less urethane groups.

For example, the urethane (meth)acrylate may be an aliphatic urethane(meth)acrylate, an aromatic urethane (meth)acrylate, or a combinationthereof. For example, the aliphatic urethane (meth)acrylate may be areaction product of an aliphatic diisocyanate, an aliphatic diol, and analiphatic hydroxy(meth)acrylate. For example, the urethane(meth)acrylate may be a reaction product of (a) a C1 to C20 aliphaticdiisocyanate, (b) a C1 to C100 aliphatic diol, and (c) a C1 to C20hydroxyalkyl(meth)acrylate. Specific examples of the aliphaticdiisocyanate are not particularly limited, and may include, for example,isophorone diisocyanate, hexamethylene diisocyanate,4,4-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate,norbomene diisocyanate, lysine diisocyanate, or a combination thereof,but is not limited thereto.

For example, the urethane (meth)acrylate may have a structurerepresented by Chemical Formula 1, but is not limited thereto.

In Chemical Formula 1,

n may be an integer of 2 to 30,

R¹ may be hydrogen or a methyl group,

R² and R³ may each independently be a substituted or unsubstituted C1 toC20 alkylene group, or a substituted or unsubstituted C3 to C20cycloalkylene group, and

R⁴ may be a substituted or unsubstituted C1 to C10 alkylene, a C2 toC100 divalent functional group including an ether, an ester, or acombination thereof, or a combination thereof.

For example, the urethane (meth)acrylate may have a weight averagemolecular weight (Mw) of about 3,000 grams per mole (g/mol) to about100,000 g/mol, for example, about 3,000 g/mol to about 50,000 g/mol, orabout 5,000 g/mol to about 10,000 g/mol. When the urethane(meth)acrylate has a weight average molecular weight within theabove-described ranges, it may have excellent transparency, flexibility,and self-healing characteristics and may show a stability to ultraviolet(UV) light. Herein, the weight average molecular weight may be measuredusing gel permeation chromatography and a polystyrene standard.

The urethane (meth)acrylate may have a glass transition temperature (Tg)of about −40° C. to about 40° C., for example about −30° C. to about 30°C., or about −20° C. to about 20° C. When the urethane (meth)acrylatehas the above-described glass transition temperature range, the urethane(meth)acrylate may show excellent transparency, flexibility, andself-healing characteristics.

The self-healing layer 13 may further include nanoparticles having adiameter of, for example, a nanometer level. For example, thenanoparticles may be particles having a diameter of about 1 nm toseveral hundred nanometers, for example, particles having diameters ofabout 1 nm to about 100 nm. The nanoparticles may be a population ofnanoparticles having an average diameter a diameter of, for example,about 1 nm to several hundred nanometers, for example, particles havingan average diameter of about 1 nm to about 100 nm.

The nanoparticles may be for example inorganic nanoparticles, organicnanoparticles, or organic/inorganic nanoparticles. The nanoparticles mayinclude, for example, silica, a metal oxide, a substituted orunsubstituted polyhedral silsesquioxane, or a combination thereof. Themetal oxide may be, for example, alumina or titanium oxide, but is notlimited thereto.

The nanoparticle may be dispersed in a polymer having a cross-linkedstructure and form a hard film to increase a surface hardness.

The self-healing layer 13 may have high elasticity and dense filmquality by including the polymer having the cross-linked structure andoptionally nanoparticles as described above. Accordingly, a surfacescratch caused by an external force may be prevented or reduced, anddamage such as a surface scratch may be self-healed in a short time.

The self-healing layer 13 may have an elastic modulus of about 0.1megapascals (MPa) to about 100 MPa. The elastic modulus may be a Young'smodulus.

The self-healing layer 13 may have a thickness of, for example, greaterthan or equal to about 50 μm. The self-healing layer 13 may have athickness of about 50 μm to about 100 μm, for example about 50 μm toabout 80 μm, or about 50 μm to about 70 μm within the range. Theself-healing layer 13 may effectively exhibit self-healing performanceby having a thickness within the above-described range.

The protective layer 12 may be disposed between the substrate 11 and theself-healing layer 13, and may be, for example a substrate protectivelayer for protecting the substrate 11. For example, the protective layer12 may prevent damage to the substrate 11 by an external force which istransferred from the surface of the laminate 10, through the surfacelayer 14 and the self-healing layer 13.

The protective layer 12 may have a greater elastic force than theself-healing layer 13, and for example, the elastic modulus of theprotective layer 12 may be greater than the elastic modulus of theself-healing layer 13. For example, the elastic modulus of theprotective layer 12 may be, for example, about 1.2 times to about 50times, about 1.2 times to about 30 times, about 1.2 times to about 20times, about 1.2 times to about 10 times, about 1.2 times to about 5times, about 1.5 times to about 30 times, about 1.5 times to about 20times, about 1.5 times to about 10 times, about 1.5 times to about 5times, about 2 times to about 30 times, about 2 times to about 20 times,about 2 times to about 10 times, or about 2 times to about 5 times,greater than the elastic modulus of the self-healing layer 13.

On the other hand, the elastic modulus of the protective layer 12 may beless than the elastic modulus of the substrate 11. Accordingly,flexibility of the laminate 10 may be ensured and thus the laminate 10may effectively be applied as a flexible window film.

The protective layer 12 is not particularly limited as long as it is amaterial having the above-described elastic modulus.

For example, the protective layer 12 may include a polymer having across-linked structure, for example a cured product of a monomer and/oran oligomer having at least one polymerizable group. The protectivelayer 12 may include for example a cured product of a multi-functionalurethane, a multi-functional epoxy, a multi-functional urea, or acombination thereof, but is not limited thereto. A cross-link density ofthe protective layer 12 may be greater than a cross-link density of theself-healing layer 13.

For example, the protective layer 12 may be a cured product of aurethane (meth)acrylate having a (meth)acrylate group and a urethanegroup, for example, and may be for example a cured product obtained bycoating a protective layer composition including a urethane(meth)acrylate having a (meth)acrylate group and a urethane group andthen curing the same. The protective layer composition may be, forexample, a photocurable composition and/or a thermally curablecomposition. The protective layer composition may be different from theself-healing composition.

For example, the urethane (meth)acrylate may have a structure having atleast two (meth)acrylate groups (CH₂═CHC(═O)O— or CH₂═C(CH₃)C(═O)O—) atthe terminal end of a core having a urethane moiety. The (meth)acrylategroup at the terminal end may be a cross-linkable functional group andmay be a kind of a chemical crosslinking site. The urethane(meth)acrylate may have a high cross-linking degree by having at leasttwo (meth)acrylate groups, whereby the cured product obtained from theprotective layer composition may have a hard film quality and highelasticity so that the substrate 11 may be effectively protected.

For example, the urethane (meth)acrylate of the protective layer 12 mayhave a number of urethane groups that is less than the number ofurethane groups in the self-healing layer 13 described above, and mayhave a structure having about 6 or less urethane groups (—NHC(═O)O—).For example, the structure of the urethane (meth)acrylate of theprotective layer 12 may have two or less diisocyanate-derived units andtwo or less diol-derived units between chemical crosslinking sites. Forexample, the urethane (meth)acrylate of the protective layer 12 mayhave, for example, about 5 or less, about 4 or less, about 3 or less,about 2 or less, or one urethane group(s).

For example, when the protective layer composition and the self-healingcomposition respectively include a urethane (meth)acrylate, the urethane(meth)acrylate included in the protective layer composition has a numberof (meth)acrylates greater than or equal to the urethane(meth)acrylateincluded in the self-healing composition, and a number of urethanegroups that is less than the urethane(meth)acrylate included in theself-healing composition. Accordingly, the protective layer 12 may isconfigured to have a higher cross-linking density than the self-healinglayer 13 and thus show a high elastic modulus as described above. Putanother way, the cured product in the protective layer 12 may have ahigher cross-link density than the self-healing layer 13 and thus show ahigh elastic modulus as described above.

For example, the urethane (meth)acrylate included in the protectivelayer composition has a weight average molecular weight (Mw) of about2,000 g/mol to about 15,000 g/mol, for example, about 3,000 g/mol toabout 10,000 g/mol, or for example, about 4,000 g/mol to about 7,000g/mol.

The protective layer 12 may further include, for example, a nanoparticleand the nanoparticle is the same as described above.

The protective layer 12, for example, may have a thickness of greaterthan or equal to about 10 μm. Thus, the protective layer 12 mayeffectively protect the substrate 11 disposed thereunder. The protectivelayer 12 may have a thickness of about 10 μm to about 100 μm, forexample, about 20 μm to about 100 μm or about 30 μm to about 80 μm.

The protective layer 12 includes a polymer having a crosslinkedstructure, and a high cross-link density as described above, and thusmay have a high elastic modulus. Accordingly, the protective layer 12may block an external force from being transferred to the substrate 11and prevent damage to the substrate 11.

The surface layer 14 may be disposed at the outermost surface of thelaminate 10 and may be, for example, a fingerprint resistance layer, ascratch resistance layer, or a hard coating layer, but is not limitedthereto.

The surface layer 14 may have a low friction coefficient and, forexample, may have a friction coefficient of less than or equal toabout 1. When the friction coefficient is within the range, the slipproperties of the surface layer may be improved. The frictioncoefficient of the surface layer 14 may be, for example, less than orequal to about 0.8, less than or equal to about 0.6, less than or equalto about 0.5, less than or equal to about 0.4, less than or equal toabout 0.3, or less than or equal to about 0.2, within the range.

The surface layer 14 may include a material having low surface energy,for example, a cured product of silicon (meth)acrylate, a cured productof fluorine (meth)acrylate, a cured product of urethane (meth)acrylate,a cured product of polyrotaxane, or a combination thereof, but is notlimited thereto.

For example, the surface layer 14 may include a cured product of silicon(meth)acrylate, and may be, for example, a cured product obtained bycoating a surface layer composition including silicon (meth)acrylate andthen curing the same. The surface layer composition may be, for example,a photocurable composition and/or a thermally curable composition.

The siloxane (meth)acrylate may include a Si—O—Si (siloxane) moiety anda meth(acrylate) group and may be a reaction product of a siloxanecompound and a (meth)acrylate-containing compound. For example, thesiloxane (meth)acrylate may be obtained by copolymerizing a siloxanecompound and a (meth)acrylate-containing compound in a solvent.

The siloxane compound may have, for example, various shapes such as achain structure, a reticular structure, and the like.

The siloxane compound may be, for example, a siloxane compound having achain structure and may be, for example, represented by Chemical Formula2.

In Chemical Formula 2,

R^(1a), R^(2a), R^(3a), R^(1b), R^(2b), R^(3b), R⁴, and R⁵ are eachindependently hydrogen, a substituted or unsubstituted C1 to C30 alkylgroup, a substituted or unsubstituted C3 to C30 cycloalkyl group, asubstituted or unsubstituted C2 to C30 heterocycloalkyl group, asubstituted or unsubstituted C6 to C30 aryl group, a substituted orunsubstituted C3 to C30 heteroaryl group, a substituted or unsubstitutedC2 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkoxygroup, or a hydroxy group, and

0≤m<1000.

The (meth)acrylate-containing compound may be a monomer having a(meth)acrylate group, an oligomer having a (meth)acrylate group, apolymer having a (meth)acrylate group, or a combination thereof. The(meth)acrylate-containing compound may include, for example, an alkyl(meth)acrylate, a hydroxyalkyl (meth)acrylate, a((meth)acryloyloxy)alkyl isocyanate, a homopolymer thereof, a copolymerthereof, or a combination thereof, but is not limited thereto. Hereinthe alkyl group may be, for example, a C1 to C30 linear or branchedalkyl, for example C1 to C10 linear or branched alkyl.

The (meth)acrylate-containing compound may include for example ahomopolymer or a copolymer including methyl (meth)acrylate, hydroxyethyl(meth)acrylate, 2-((meth)acryloyloxy)ethyl isocyanate, or a combinationthereof. The (meth)acrylate-containing compound may be for example acopolymer of poly(methyl (meth)acrylate) or methyl (meth)acrylate,hydroxyethyl (meth)acrylate, and 2-((meth)acryloyloxy)ethyl isocyanate,but is not limited thereto. The (meth)acrylate-containing compound maybe for example a copolymer of methyl (meth)acrylate, hydroxyethyl(meth)acrylate and 2-((meth)acryloyloxy)ethyl isocyanate, and thecopolymer may be for example obtained by copolymerizing methyl(meth)acrylate with hydroxyethyl (meth)acrylate and then introducing2-((meth)acryloyloxy)ethyl isocyanate by a grafting reaction. Herein, anamount of hydroxyethyl (meth)acrylate and 2-((meth)acryloyloxy)ethylisocyanate may be each independently about 5 weight percent (wt %) toabout 15 wt %.

The siloxane compound and the (meth)acrylate-containing compound may beincluded in a weight ratio of about 20:80 to about 50:50. When thesiloxane compound and the (meth)acrylate-containing compound areincluded within the ratio range, high transparency and surface hardnessmay be effectively ensured.

The siloxane (meth)acrylate may have a weight average molecular weight(Mw) as measured by a gel permeation chromatography (GPC) using apolystyrene standard, of about 50,000 g/mol to about 400,000 g/mol, forexample about 100,000 g/mol to about 300,000 g/mol.

For example, the surface layer 14 may include a cured product offluorine (meth)acrylate, and may be for example a cured product obtainedby coating a surface layer composition including fluorine (meth)acrylateand then curing the same. The surface layer composition may be forexample a photocurable composition, a thermally curable composition, ora combination thereof.

The fluorine (meth)acrylate may be (meth)acrylate including at least onefluorine, for example a monofluoro-, difluoro-, trifluoro- or higheralkyl (meth)acrylate, or a perfluoroalkyl (meth)acrylate where the alkylgroup may be, for example, a C1 to C30 linear or branched alkyl, forexample C1 to C10 linear or branched alkyl. The surface layercomposition including the fluorine (meth)acrylate may further include asiloxane compound.

For example, the surface layer 14 may include a cured product ofpolyrotaxane and may be for example a cured product obtained by coatinga surface layer composition including polyrotaxane and then curing thesame.

The polyrotaxane may refer to a compound having a mechanicallyinterlocked polymer architecture consisting of a dumbbell shapedmolecule which is threaded through a macrocycle. The polyrotaxane mayinclude a cyclic molecule, a linear molecule penetrating a ring of thecyclic molecule, and a capping group at both terminal ends of the linearmolecule. The polyrotaxane may be move flexibly in response to externalpressure to provide good flexibility and may be highly stretched.

In the polyrotaxane, the cyclic molecule may be a cyclic molecule havinga hydroxyl group and may be for example a cyclodextrin-based compound,specifically, a compound including α-cyclodextrin, β-cyclodextrin,γ-cyclodextrin, or a combination thereof.

For example, the polyrotaxane may have a curable functional group at theterminal end of the cyclic molecule. For example, the cyclic moleculemay be a cyclodextrin-based compound having a structure in which aportion or all of the hydroxyl groups of the cyclodextrin is substitutedwith a functional group including a curable functional group. Thepolyrotaxane including the cyclic molecule may have an appropriatehardness and flexibility, and so may be applied for the curable film.

The curable functional group may be a functional group that may be curedby a reaction with light, for example a (meth)acrylate, a vinyl group,an allyl group, a hydroxyl group, a cyanate group, a thiol group, or acombination thereof, but is not limited thereto. The cyclic molecule mayinclude at least one curable functional group, for example two or more,or six or less, or four or less curable functional groups.

For example, the cyclic molecule may be a cyclodextrin-based compoundincluding (meth)acrylate groups at both terminal ends.

The curable functional group may be substituted directly ontocyclodextrin or may be substituted via a linking group such as a poly(C1to C20 alkylene), a poly(C1 to C20 alkylene glycol), or apolycaprolactone, and the like. That is, the cyclic molecule may be acyclodextrin-based compound substituted with a poly(C1 to C20 alkylene)having a curable functional group at a terminal end, a poly(C1 to C20alkylene glycol) having a curable functional group at a terminal end, ora polycaprolactone having a curable functional group at a terminal end.For example, the cyclic molecule may be cyclodextrin substituted withpolycaprolactone having a (meth)acrylate group at a terminal end.

In the polyrotaxane, the linear molecule may include, for example,polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene,polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane,polyethylene, polypropylene, or a combination thereof, and in this case,the linear molecule of the polyrotaxane is stable when exposed toultraviolet (UV) and has improved optical properties. A molecular weightof the linear molecule may be greater than or equal to about 10,000g/mol, or greater than or equal to about 30,000 g/mol and less than orequal to about 500,000 g/mol.

The capping groups are positioned at each of the terminal ends of thelinear molecule to prevent the escape from the cyclic molecule, and forexample, may be selected from a dinitrophenyl, a cyclodextrin, anadamantane, a trityl, a fluorescein, a pyrene, a benzene, a polynucleararomatic, a steroid, or a combination thereof, each of which may beindependently substituted or unsubstituted with a C1 to C20 alkyl group,a hydroxyl group, a halogen group, a cyano group, sulfonyl group, acarboxyl group, an amino group, a phenyl group, or a combinationthereof.

A weight average molecular weight of the polyrotaxane may be greaterthan or equal to about 100,000 g/mol and less than or equal to about5,000,000 g/mol, for example greater than or equal to about 500,000g/mol and less than or equal to about 3,000,000 g/mol, or greater thanor equal to about 800,000 g/mol and less than or equal to about2,000,000 g/mol. The weight average molecular weight may be analyzed bya gel permeation chromatography (GPC).

The surface layer 14 may further include, for example, a nanoparticleand the nanoparticle is the same as described above.

For example, the surface layer 14 may include a cured product of thepolyrotaxane, a cured product of the fluorine (meth)acrylate, and acured product of the polyhedral silsesquioxane.

The surface layer 14 may be thinner than each of the protective layer 12and the self-healing layer 13, and may have a thickness of, for exampleabout 20 nm to about 300 nm. Within the range, the surface layer 14 mayhave a thickness of, for example about 30 nm to about 250 nm thickness,about 50 nm to about 200 nm, or about 60 nm to about 150 nm.

The laminate 10 may further include at least one additional layer (notshown).

The laminate 10 may have a high water contact angle. Accordingly, thelaminate 10 may have sufficient slip properties and good waterrepellency. The laminate 10 may have for example a contact angle ofgreater than or equal to about 100 degrees)(°), for example, a contactangle of greater than or equal to about 105°, greater than or equal to110°, or greater than or equal to 115°. Herein, the contact angle may bemeasured by using a Sessile drop technique. The contact angle may bemeasured by using water as a liquid and a drop shape analyzer (DSA100,KRUSS, Germany) and dripping a predetermined amount (about 15 ml) ofwater on the surface layer 14 of the laminate 10.

The laminate 10 may have for example pencil hardness of greater than orequal to about 6 H, for example, greater than or equal to about 7 H, andfor example, greater than or equal to about 8 H within the range.Herein, the pencil hardness may be measured according to ASTM D3363 andmay be a maximum pencil hardness at which a scratch is no longer visibleafter 3 minutes at 50° C. following formation of the scratch with a loadof 1 kg.

The laminate 10 may, for example, have a light transmittance of greaterthan or equal to about 85%, a yellowness index of less than about 1, andhaze of less than about 1.

In this way, the laminate 10 includes the protective layer 12, theself-healing layer 13, and the surface layer 14, which are sequentiallylaminated on the substrate 11, and thus may effectively reduce a damageto the substrate 11, be self-healed from a surface scratch at roomtemperature within a short period of time, and reinforce slipcharacteristics. Accordingly, the mechanical characteristics and surfacecharacteristics of the laminate 10 may be simultaneously satisfied.

The laminate 10 may be a transparent film, for example a transparentflexible film.

The laminate 10 may be usefully applied to a plate or a window film forwhich transparency and flexibility are beneficial. For example, thelaminate 10 may be effectively applied to a window film for anelectronic device, for example, a window film for a display device. Forexample, the laminate 10 may be attached on a surface of the displaypanel and the display panel and the laminate 10 may be bonded directlyor through an intervening adhesive. The display panel may be, forexample, a liquid crystal display panel or an organic light emittingdisplay panel, but is not limited thereto. The laminate 10 may bedisposed at a side facing a viewer.

FIG. 2 is a cross-sectional view of a display device according to anembodiment.

Referring to FIG. 2, a display device 100 according to an embodimentincludes a display panel 50 and a window film 10A.

The display panel 50 may be for example an organic light emittingdisplay (OLED) panel or a liquid crystal display (LCD) panel, and maybe, for example, a bendable display panel, a foldable display panel, arollable display panel, or a combination thereof.

The window film 10A may include the above-described laminate and may bedisposed at a side facing a viewer. An additional layer may be disposedbetween the display panel 50 and the window film 10A. For example asingle layer or plurality of polymer layers (not shown) and optionally atransparent adhesion layer (not shown) may be further included.

FIG. 3 is a cross-sectional view of a display device according toanother embodiment.

Referring to FIG. 3, the display device according to an embodimentincludes a display panel 50, a window film 10A, and a touch screen panel70 disposed between the display panel 50 and the window film 10A.

The display panel 50 may be, for example, an organic light emittingdisplay panel or a liquid crystal display panel, for example a bendabledisplay panel, a foldable display panel, a rollable display panel, or acombination thereof.

The window film 10A may include the above-described laminate and may bedisposed at a side of a viewer.

The touch screen panel 70 may be disposed adjacent to each of the windowfilm 10A and the display panel 50 to recognize the touched position andthe position change when touched by a human hand or a tool through thewindow film 10A, and then to output a touch signal. The driving module(not shown) may monitor a position where the touch screen panel 70 istouched based on the output touch signal; recognize an icon marked atthe touched position; and control the device to carry out thefunction(s) corresponding to the recognized icon, and display thefunction performance results on the display panel 50.

An additional layer or layers may be disposed between the touch screenpanel 70 and the window film 10A. For example a single polymer layer orplurality of polymer layers (not shown), and optionally a transparentadhesion layer (not shown), may be further included.

Another layer may be disposed between the touch screen panel 70 and thedisplay panel 50. For example a single polymer layer or a plurality oflayers polymer layers (not shown), and optionally a transparent adhesionlayer (not shown), may be further included.

The laminate 10, or the window film 10A including the same, may beapplied to a variety of electronic devices such as a smart phone, atablet PC, a camera, a touch screen device, and so on, but is notlimited thereto.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. However, these examples are exemplary, and thepresent disclosure is not limited thereto.

PREPARATION OF COMPOSITION PREPARATION EXAMPLE 1

81 g (0.154 mol) of polycaprolactone diol (PCL 205 U, Daicel Corp.),5.948 g (0.066 mol) of butanediol, 65.365 g (0.2941 mol) of isophoronediisocyanate, and 73.5 g of ethyl acetate are put in a 3-neck flask in anitrogen atmosphere and then heated up to 70° C. Upon reaching 70° C.,the temperature is constantly maintained, and the mixture is reacted for3 hours, with stirring. The temperature is decreased down to 60° C., and19.183 g (0.1474 mol) of hydroxypropyl acrylate is added thereto, andthe obtained mixture is additionally reacted for 2 hours with stirring,and a solution obtained therefrom is cooled down to obtain a urethaneacrylate oligomer. The obtained urethane acrylate shows a peak at 2270cm⁻¹ (as measured by infrared ray spectroscopic analysis) correspondingto an isocyanate group, and has a weight average molecular weight ofabout 6,500 g/mol and a glass transition temperature (Tg) of 10° C. Theurethane acrylate has a structure including eight urethane groups and anacrylate group at each terminal end, and herein, a mole ratio ofdiisocyanate to diol to acrylate is 4:3:2. The urethane acrylate has astructure having eight urethane groups and two acrylate groups.

Subsequently, a photoinitiator (Irgacure 184) and trisilanolphenyl POSS(Hybrid Plastics Inc.), each in an amount of 0.5 wt % based on the totalweight of a solid in the urethane acrylate solution, are added to theurethane acrylate solution and mixed therewith to prepare a composition.

PREPARATION EXAMPLE 2

81 g (0.154 mol) of polycaprolactonediol (PCL 205 U, Daicel Corp.),5.948 g (0.066 mol) of butanediol, 73.359 g (0.33 mol) of isophoronediisocyanate, and 80 g of ethyl acetate are put and mixed in a 3-neckflask in a nitrogen atmosphere and then, heated up to 70° C.Subsequently, upon reaching 70° C., the temperature is constantlymaintained, and the obtained mixture is reacted for 3 hours, withstirring. The temperature is decreased down to 60° C., then, 28.631 g(0.22 mol) of hydroxypropyl acrylate is added thereto, the obtainedmixture is additionally reacted for 2 hours, and a solution obtainedtherefrom is cooled down to obtain a urethane acrylate oligomer. Theobtained urethane acrylate shows a peak at 2270 cm⁻¹ corresponding to anisocyanate group in an infrared ray spectroscopic analysis, and has aweight average molecular weight of about 4600 g/mol and a glasstransition temperature (Tg) of 17° C. The urethane acrylate has astructure including six urethane groups positioned between an acrylategroup at each of the terminal ends, and herein, a mole ratio ofdiisocyanate to diol to acrylate is 3:2:2. The urethane acrylate has astructure having six urethane groups and two acrylate groups.

A photoinitiator (Irgacure 184) and trisilanolphenyl POSS (HybridPlastics Inc.), each in an amount of 0.5 wt % based on the total weightof a solid in the urethane acrylate solution, are added to the urethaneacrylate solution and mixed therewith to prepare a composition.

PREPARATION EXAMPLE 3

35 wt % of polyrotaxane (SM-3403P, Advanced Softmaterials Inc.)including a cyclodextrin cyclic molecule substituted with apolycaprolactone functional group having a methacrylate group at theterminal end, a polyethylene glycol-based linear molecule penetrating aring of the cyclodextrin cyclic molecule, and an adamantane cappinggroup at both of the terminal ends of the linear molecule, and inaddition, having a molecular weight of about 1,000,000 g/mol, iscombined with 33 wt % of acryl polyhedral silsesquioxane (HybridPlastics Inc.), 1 wt % of fluorinated propyl polyhedral silsesquioxane(Hybrid Plastics Inc.), 16 wt % of trisilanolphenyl polyhedralsilsesquioxane (Hybrid Plastics Inc.), 9 wt % of a fluorinated acrylcompound (KY-1203, Shin-Etsu Chemical Co., Ltd.), 4 wt % of asilicon-based acryl compound (FM-7725, JNC Co.), and 2 wt % of aphotoinitiator (Irgacure 184, Ciba) to prepare a composition.

MANUFACTURE OF LAMINATE EXAMPLE 1

The composition according to Preparation Example 2 is coated on a 100μm-thick polyethylene terephthalate (PET) film (elastic modulus: 2.3GPa), dried at 80° C. for 10 minutes, and ultraviolet (UV) light-curedfor 3 seconds to form a 60 μm-thick substrate protective layer.

Subsequently, the composition according to Preparation Example 1 iscoated on the protective layer, dried at 80° C. for 10 minutes, andultraviolet (UV) light-cured for 2 minutes to form a 60 μm-thickself-healing layer.

On the self-healing layer, the composition according to PreparationExample 3 is coated, dried at 120° C. for 1 minute, and ultraviolet (UV)light-cured to form a 60 nm-thick surface layer to manufacture alaminate.

EXAMPLE 2

A laminate is manufactured according to the same method as Example 1,except for forming the surface layer to be 300 nm thick.

EXAMPLE 3

A laminate is manufactured according to the same method as Example 1,except for forming the self-healing layer to be 100 μm thick.

COMPARATIVE EXAMPLE 1

A laminate is manufactured according to the same method as Example 1,except for not forming the substrate protective layer and the surfacelayer.

COMPARATIVE EXAMPLE 2

A laminate is manufactured according to the same method as Example 1,except for not forming the substrate protective layer.

COMPARATIVE EXAMPLE 3

A laminate is manufactured according to the same method as Example 1,except for not forming the surface layer.

COMPARATIVE EXAMPLE 4

A laminate is manufactured according to the same method as Example 1,except for forming the substrate protective layer by using thecomposition according to Preparation Example 1 instead of thecomposition according to Preparation Example 2 and forming theself-healing layer by using the composition according to PreparationExample 2 instead of the composition according to Preparation Example 1.

COMPARATIVE EXAMPLE 5

A laminate is manufactured according to the same method as Example 1,except for forming the substrate protective layer by using thecomposition according to Preparation Example 1 instead of thecomposition according to Preparation Example 2.

COMPARATIVE EXAMPLE 6

A laminate is manufactured according to the same method as Example 1,except for forming the self-healing layer to be 10 μm thick.

COMPARATIVE EXAMPLE 7

A laminate is manufactured according to the same method as Example 1,except for forming the self-healing layer to be 30 μm thick.

COMPARATIVE EXAMPLE 8

A laminate is manufactured according to the same method as Example 1,except for forming the surface layer to be 10 nm thick.

COMPARATIVE EXAMPLE 9

A laminate is manufactured according to the same method as Example 1,except for forming the surface layer to be 500 nm thick.

Evaluation Evaluation I

An elastic modulus of each layer in the laminates according to theExamples and the Comparative Examples is measured.

The elastic modulus is measured by preparing each specimen having a sizeof 10 mm×10 mm×5 mm and using dynamic mechanical analysis (DMA)(SDTA861, Mettler-Toledo (S) Pte Ltd.).

The results are shown in Table 1.

TABLE 1 Substrate protective Self-healing layer layer (MPa) (MPa)Examples 1, 2, and 3 7.5 2.5 Comparative Examples 3 and 6 to 9Comparative Example 1 — 2.5 Comparative Example 2 — 2.5 ComparativeExample 4 2.5 7.5 Comparative Example 5 2.5 2.5

Evaluation II

A friction coefficient of the laminates according to the Examples andthe Comparative Examples is measured.

The friction coefficient is measured by using a friction-measuringinstrument (FPT-F1, Labthink Instruments Co., Ltd.).

The results are shown in Table 2.

TABLE 2 Friction Coefficient Example 1, 2, and 3 0.15 ComparativeExamples 1 and 3 1.3 

Evaluation III

The friction coefficient, a contact angle, and self-healing pencilhardness of the laminates according to the Examples and the ComparativeExamples are evaluated.

The contact angle is measured by a Sessile drop technique, performed bydropping water on each laminate with a Drop shape analyzer (DSA100,KRUSS, Germany) and using a Sessile drop technique.

The self-healing pencil hardness is evaluated by fixing each laminate ona 2 mm-thick glass plate, scratching the laminate with a pencil under avertical load of 1 kg at 60 millimeters per minute (mm/min), and findinga maximum pencil hardness at which the scratch is no longer visibleafter 3 minutes at 50° C., as visually observed with the naked eye.Herein, the self-healing pencil hardness is measured by using anautomatic pencil scratch hardness tester (No. 553-M1, YASUDA SEIKISEISAKUSHO LTD.) and a Mitsubishi pencil according to ASTM D3363standard.

The results are shown in Table 3.

TABLE 3 Self-healed or not Contact angle Self-healing after scratch with(degree) pencil hardness 8H pencil Example 1 115   8H ⊚ Example 2 115  8H ⊚ Example 3 115   6H ◯ Comparative Example 1  91 <2H X ComparativeExample 2 115 <2H X Comparative Example 3  91   4H X Comparative Example4 115 <2H X Comparative Example 5 115 <2H X Comparative Example 6 115<1H X Comparative Example 7 115   2H X Comparative Example 8 113 <2H XComparative Example 9 115 <2H X ⊚: no scratch, ◯: almost no scratch (afew minute scratches), X: a distinct scratch

Referring to Table 3, the laminates according to the Examples show ahigh contact angle and have a high self-healing pencil hardness comparedwith the laminates according to the Comparative Examples. In particular,Examples 1 to 3 and Comparative Examples 4 and 5 show differentself-healing properties and the presence of damage (or not) on asubstrate depends on an elastic modulus of a self-healing layer and aprotective layer. Accordingly, the laminates according to Examples 1 to3 show improved surface characteristics such as slip properties,self-healing properties, and mechanical characteristics compared withthe laminates according to Comparative Examples 1 to 9.

While this disclosure has been described in connection with what ispresently considered to be practical example embodiments, it is to beunderstood that the invention is not limited to the disclosedembodiments, but, on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

What is claimed is:
 1. A display device comprising: a display panel, anda window film, the window film including a substrate, a protective layeron the substrate, a self-healing layer on the protective layer, athickness of the self-healing layer being greater than or equal to about50 micrometers, and a surface layer on the self-healing layer, whereinan elastic modulus of the protective layer is greater than an elasticmodulus of the self-healing layer, and a friction coefficient of thesurface layer is less than or equal to about
 1. 2. The display device ofclaim 1, wherein the elastic modulus of the protective layer is about1.2 times to about 50 times greater than the elastic modulus of theself-healing layer.
 3. The display device of claim 1, wherein theelastic modulus of the self-healing layer is about 0.1 megapascals toabout 100 millipascals.
 4. The display device of claim 1, wherein theelastic modulus of the protective layer is less than an elastic modulusof the substrate.
 5. The display device of claim 1, wherein the surfacelayer is thinner than the protective layer and the self-healing layer.6. The display device of claim 1, wherein a thickness of the surfacelayer is about 20 nanometers to about 300 nanometers.
 7. The displaydevice of claim 1, wherein a thickness of the protective layer is about20 micrometers to about 100 micrometers, and a thickness of theself-healing layer is about 50 micrometers to about 100 micrometers. 8.The display device of claim 1, wherein the protective layer and theself-healing layer each comprise a polymer having a cross-linkedstructure, and a cross-link density of the protective layer is greaterthan cross-link density of the self-healing layer.
 9. The display deviceof claim 1, wherein the protective layer and the self-healing layer eachindependently comprise a cured product of a multi-functional urethane, acured product of a multi-functional epoxy, a cured product of amulti-functional urea, or a combination thereof.
 10. The display deviceof claim 1, wherein the self-healing layer comprises a cured product ofa first urethane (meth)acrylate comprising a (meth)acrylate group and atleast six urethane groups.
 11. The display device of claim 10, whereinthe self-healing layer further comprises silica, a metal oxide, asubstituted or unsubstituted polyhedral silsesquioxane, or a combinationthereof.
 12. The display device of claim 10, wherein the protectivelayer comprises a cured product of a second urethane (meth)acrylatecomprising at least two (meth)acrylate groups and at least one urethanegroup, wherein the number of the urethane groups in the second urethane(meth)acrylate is less than the number of the urethane groups in thefirst urethane (meth)acrylate.
 13. The display device of claim 12,wherein the protective layer further comprises silica, a metal oxide, asubstituted or unsubstituted polyhedral silsesquioxane, or a combinationthereof.
 14. The display device of claim 1, wherein the surface layercomprises a cured product of silicon (meth)acrylate, a cured product ofa fluorine (meth)acrylate, a cured product of a urethane (meth)acrylate,a cured product of a polyrotaxane, or a combination thereof.
 15. Thedisplay device of claim 14, wherein the surface layer further comprisessilica, a metal oxide, a substituted or unsubstituted polyhedralsilsesquioxane, or a combination thereof.
 16. The display device ofclaim 1, wherein the surface layer comprises a cured product ofpolyrotaxane, a cured product of a fluorine (meth)acrylate, and a curedproduct of a polyhedral silsesquioxane.
 17. The display device of claim1, wherein the substrate comprises polyethylene terephthalate,polycarbonate, polyimide, polyamide, polyamideimide, or a combinationthereof.
 18. The display device of claim 1, wherein the display panel isan organic light emitting display panel or a liquid crystal displaypanel.
 19. The display device of claim 1, further comprising a touchscreen panel between the display panel and the window film.
 20. Anelectronic device comprising the display device of claim 1.